Marine calcifiers are considered to be among the most vulnerable taxa to climate-forced environmental changes occurring on continental margins with effects hypothesized to occur on microstructural, biomechanical, and geochemical properties of carbonate structures. Natural gradients in temperature, salinity, oxygen, and pH on an upwelling margin combined with the broad depth distribution (100-1,100 m) of the pink fragile sea urchin, Strongylocentrotus (formerly Allocentrotus) fragilis, along the southern California shelf and slope provide an ideal system to evaluate potential effects of multiple climate variables on carbonate structures in situ. We measured, for the first time, trait variability across four distinct depth zones using natural gradients as analogues for species-specific implications of oxygen minimum zone (OMZ) expansion, deoxygenation and ocean acidification. Although S. fragilis may likely be tolerant of future oxygen and pH decreases predicted during the twenty-first century, we determine from adults collected across multiple depth zones that urchin size and potential reproductive fitness (gonad index) are drastically reduced in the OMZ core (450-900 m) compared to adjacent zones. Increases in porosity and mean pore size coupled with decreases in mechanical nanohardness and stiffness of the calcitic endoskeleton in individuals collected from lower pH(Total) (7.57-7.59) and lower dissolved oxygen (13-42 mu mol kg(-1)) environments suggest that S. fragilis may be potentially vulnerable to crushing predators if these conditions become more widespread in the future. In addition, elemental composition indicates that S. fragilis has a skeleton composed of the low Mg-calcite mineral phase of calcium carbonate (mean Mg/Ca = 0.02 mol mol(-1)), with Mg/Ca values measured in the lower end of values reported for sea urchins known to date. Together these findings suggest that ongoing declines in oxygen and pH will likely affect the ecology and fitness of a dominant echinoid on the California margin.

Basaltic lavas erupted at some oceanic intraplate hotspot volcanoes are thought to sample ancient subducted crustal materials(1,2). However, the residence time of these subducted materials in the mantle is uncertain and model-dependent(3), and compelling evidence for their return to the surface in regions of mantle upwelling beneath hotspots is lacking. Here we report anomalous sulphur isotope signatures indicating mass-independent fractionation (MIF) in olivine-hosted sulphides from 20-million-year-old ocean island basalts from Mangaia, Cook Islands (Polynesia), which have been suggested to sample recycled oceanic crust(3,4). Terrestrial MIF sulphur isotope signatures (in which the amount of fractionation does not scale in proportion with the difference in the masses of the isotopes) were generated exclusively through atmospheric photochemical reactions until about 2.45 billion years ago(5-7). Therefore, the discovery of MIF sulphur in these young plume lavas suggests that sulphur-probably derived from hydrothermally altered oceanic crust-was subducted into the mantle before 2.45 billion years ago and recycled into the mantle source of Mangaia lavas. These new data provide evidence for ancient materials, with negative Delta S-33 values, in the mantle source for Mangaia lavas. Our data also complement evidence for recycling of the sulphur content of ancient sedimentary materials to the subcontinental lithospheric mantle that has been identified in diamond-hosted sulphide inclusions(8,9). This Archaean age for recycled oceanic crust also provides key constraints on the length of time that subducted crustal material can survive in the mantle, and on the timescales of mantle convection from subduction to upwelling beneath hotspots.

Volatile elements have a fundamental role in the evolution of planets. But how budgets of volatiles were set in planets, and the nature and extent of volatile-depletion of planetary bodies during the earliest stages of Solar System formation remain poorly understood(1,2). The Moon is considered to be volatile-depleted and so it has been predicted that volatile loss should have fractionated stable isotopes of moderately volatile elements(3). One such element, zinc, exhibits strong isotopic fractionation during volatilization in planetary rocks(4,5), but is hardly fractionated during terrestrial igneous processes(6), making it a powerful tracer of the volatile histories of planets. Here we present high-precision zinc isotopic and abundance data which show that lunar magmatic rocks are enriched in the heavy isotopes of zinc and have lower zinc concentrations than terrestrial or Martian igneous rocks. Conversely, Earth and Mars have broadly chondritic zinc isotopic compositions. We show that these variations represent large-scale evaporation of zinc, most probably in the aftermath of the Moon-forming event, rather than small-scale evaporation processes during volcanism. Our results therefore represent evidence for volatile depletion of the Moon through evaporation, and are consistent with a giant impact origin for the Earth and Moon.

New major- and trace-element abundances, highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances, and oxygen and rhenium-osmium isotope data are reported for oligoclase-rich meteorites Graves Nunataks 06128 and 06129 (GRA 06128/9), six brachinites (Brachina; Elephant Morraine 99402/7; Northwest Africa (NWA) 1500; NWA 3151; NWA 4872; NWA 4882) and three olivine-rich achondrites, which are referred to here as brachinite-like achondrites (NWA 5400; NWA 6077; Zag (b)). GRA 06128/9 represent examples of felsic and highly-sodic melt products from an asteroid that may provide a differentiation complement to brachinites and/or brachinite-like achondrites. The new data, together with our petrological observations, are consistent with derivation of GRA 06128/9, brachinites and the three brachinite-like achondrites from nominally volatile-rich and oxidised 'chondritic' precursor sources within their respective parent bodies. Furthermore, the range of Delta O-17 values (similar to 0 parts per thousand to -0.3 parts per thousand) among the meteorites indicates generation from isotopically heterogeneous sources that never completely melted, or isotopically homogenised. It is possible to generate major-and trace-element compositions similar to brachinites and the three studied brachinite-like achondrites as residues of moderate degrees (13-30%) of partial melting of primitive chondritic sources. This process was coupled with inefficient removal of silica-saturated, high Fe/Mg felsic melts with compositions similar to GRA 06128/9. Melting of the parent bodies of GRA 06128/9, brachinites and brachinite-like achondrites halted well before extensive differentiation, possibly due to the exhaustion of the short-lived radionuclide Al-26 by felsic melt segregation. This mechanism provides a potential explanation for the cessation of run-away melting in asteroids to preserve achondrites such as GRA 06128/9, brachinites, brachinite-like achondrites, acapulcoite-lodranites, ureilites and aubrites. Moderate degrees of partial melting of chondritic material and generation of Fe-Ni-S-bearing melts are generally consistent with HSE abundances that are within factors of similar to 2-10 x CI-chondrite abundances for GRA 06128/9, brachinites and the three brachinite-like achondrites. However, in detail, brachinite-like achondrites NWA 5400, NWA 6077 and Zag (b) are interpreted to have witnessed single-stage S-rich metal segregation, whereas HSE in GRA 06128/9 and brachinites have more complex heritages. The HSE compositions of GRA 06128/9 and brachinites require either: (1) multiple phases in the residue (e. g., metal and sulphide); (2) fractionation after generation of an initial melt, again involving multiple phases; (3) fractional fusion, or; (4) a parent body with non-chondritic relative HSE abundances. Petrological and geochemical observations permit genetic links (i.e., same parent body) between GRA 06128/9 and brachinites and similar formation mechanisms for brachinites and brachinite-like achondrites. (C) 2011 Elsevier Ltd. All rights reserved.

Plate tectonic processes result in recycling of crust and lithosphere into Earth's mantle. Evidence for long-term preservation of recycled reservoirs in the mantle comes from the enriched isotopic character of oceanic island basalt (OIB) lavas. Although recycled constituents can explain much of the geochemical variation in the OIB-source mantle, it has been shown that direct melting of these components would lead to magmas with evolved compositions, unlike OIB. Instead, it has been argued that either metasomatic pyroxene-rich peridotite that has inherited the trace element and isotopic character of subducted materials, or high-temperature intramantle metasomatism of lithosphere can explain OIB compositions. To test these models, we present new oxygen and osmium isotope data for lavas from the Canary Islands of El Hierro and La Palma. These islands have distinct (18)O/(16)O and (187)Os/(188)Os compositions that can be explained through melting of pyroxenite-enriched peridotite mantle containing <10% recycled oceanic lithosphere. We also assess O-Os isotope systematics of lavas from Hawai'i and the Azores and show that they also conform to addition of distinct recycled oceanic components, including lithosphere and pelagic sediment. We conclude that enriched isotopic signatures of some OIBs are consistent with pyroxenite-rich mantle sources metasomatized by recycled components.

Miller Range (MIL) 05035 is a low-Ti mare basalt that consists predominantly of pyroxene (62.3 vol%) and plagioclase (26.4 vol%). Pyroxenes are strongly shocked and complexly zoned from augite (Wo(33)) and pigeonite (Wo(17)) cores with Mg# = 50-54 to hedenbergite rims. Coexisting pyroxene core compositions reflect crystallization temperatures of 1000 to 1100 degrees C. Plagioclase has been completely converted to maskelynite with signs of recrystallization. Maskelynite is relatively uniform in composition (An(94)Ab(6)-An(91)Ab(9)), except at contacts with late-stage mesostasis areas (elevated K contents, An(82)Ab(15)Or(3)). Symplectites (intergrowth of Fe-augite, fayalite, and silica) of different textures and bulk compositions in MIL 05035 suggest formation by decomposition of Ferro-pyroxene during shock-induced heating, which is Supported by the total maskelynitization of plagioclase, melt pockets, and the presence of a relict pyroxferroite grain. Petrography and mineral chemistry imply that crystallization of MIL 05035 Occurred in the sequence of Fe-poor pyroxenes (Mg# = 50-54), followed by plagioclase and Fe-rich pyroxenes (Mg# = 20-50), and finally hedenbergite, Fe-Ti oxides, and minor late-stage phases. Petrography, bulk chemistry, mineral compositions, and the age of MIL 05035 Suggest it is possibly Source crater-paired with Asuka (A-) 881757 and Yamato (Y-) 793169, and may also be launch-paired with Meteorite Hills (MET) 01210. MIL 05035 represents an old (similar to 3.8-3.9 Ga), incompatible element-depleted low-Ti basalt that was not sampled during the Apollo or Luna missions. The light-REE depleted nature and lack of Eu anomalies For this meteorite are consistent with an origin distant from the Procellarum KREEP Terrane, and genesis from an early Cumulate mantle-source region generated by extensive differentiation of the Moon.

A new combined rhenium-osmium- and platinum-group element data set for basalts from the Moon establishes that the basalts have uniformly low abundances of highly siderophile elements. The data set indicates a lunar mantle with long-term, chondritic, highly siderophile element ratios, but with absolute abundances that are over 20 times lower than those in Earth's mantle. The results are consistent with silicate-metal equilibrium during a giant impact and core formation in both bodies, followed by post-core-formation late accretion that replenished their mantles with highly siderophile elements. The lunar mantle experienced late accretion that was similar in composition to that of Earth but volumetrically less than (similar to 0.02% lunar mass) and terminated earlier than for Earth.

Quantitative textural data for Northwest Africa (NWA) 032 and the LaPaz (LAP) mare basalt meteorites (LAP 02205, LAP 02224, LAP 02226, and LAP 02436) provide constraints on their crystallization and mineral growth histories. In conjunction with whole-rock and mineral chemistry, textural analysis provides powerful evidence for meteorite pairing. Petrographic observations and crystal size distribution (CSD) measurements of NWA 032 indicate a mixed population of slowly cooled phenocrysts and faster cooled matrix. LaPaz basalt crystal populations are consistent with a single phase of nucleation and growth. Spatial distribution patterns (SDP) of minerals in the meteorites highlight the importance of clumping and formation of clustered crystal frameworks in their melts, succeeded by continued nucleation and growth of crystals. This process resulted in increasingly poor sorting, during competition for growth, as the melt crystallized. Based on CSD and SDP data, we suggest a potential lava flow geometry model to explain the different crystal populations for NWA 032 and the LaPaz basalts. This model involves crystallization of early formed phenocrysts at hypabyssal depths in the lunar crust, followed by eruption and flow differentiation on the lunar surface. Lava flow differentiation would allow for formation of a cumulate base and facilitate variable cooling within the stratigraphy, explaining the varied textures and modal mineralogies of mare basalt meteorites. The model may also provide insight into the relative relationships of some Apollo mare basalt suites, shallow-level crystal fractionation processes, and the nature of mare basalt volcanism over lunar history.

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of delta O-18 values (-0.5 to 22.9 parts per thousand) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; lambda = 0.5259 +/- 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Delta O-17 for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01 parts per thousand and are indistinguishable from the TFL. The delta O-18 values of high- and low-Ti lunar basalts are distinct. Average whole-rock delta O-18 values for low-Ti lunar basalts from the Apollo 12 (5.72 +/- 0.06 parts per thousand) and Apollo 15 landing sites (5.65 +/- 0.12 parts per thousand) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 +/- 0.11 parts per thousand). Evolved low-Ti LaPaz mare-basalt meteorite delta O-18 values (5.67 +/- 0.05 parts per thousand) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in delta O-18 do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine-pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average delta O-18 (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Delta=0.18 parts per thousand) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the delta O-18 of lunar mantle olivine in this study are only 0.05 parts per thousand higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth-Moon system. (c) 2006 Elsevier B.V. All rights reserved.

Antarctic lunar meteorites Meteorite Hills 01210 and Pecora Escarpment 02007 are breccias that come from different regolith lithologies on the Moon. MET 01210 is composed predominantly of fractionated low-Ti basaltic material and is classified as an immature, predominantly basaltic glassy matrix regolith breccia. PCA 02007 is a predominantly feldspathic regolith breccia consisting of metamorphosed feldspathic, noritic, troctolitic and noritic-anorthosite clasts, agglutinate and impact-glasses, as well as a number of basaltic clasts with mare and possible non-mare affinities. The basalt clasts in MET 0 12 10 have undergone 'Fenner' trend enrichments in iron and may also have witnessed late-stage crystallization of zircon or a zirconium-rich mineral. Some of the features of MET 0 1210 are similar to other basaltic lunar breccia meteorites (e.g., Northwest Africa 773; Elephant Moraine 87521/96008; Yamato 793274/981031), but it is not paired with them. The presence of metamorphic anorthositic clasts as well as agglutinates indicates a small regolith component. Similarities with previously discovered evolved (e.g., LaPaz Icefield 02205; Northwest Africa 032) and ferroan (e.g., Asuka 881757; Yamato 793169) basaltic lunar meteorites suggest a similar mare source region for MET 01210. Despite lack of evidence for pairing, PCA 02007 shares many features with other feldspathic regolith breccias (e.g., Yamato 791197, Queen Alexandra Range 94281), including a high Mg/Fe whole-rock composition, glass spherules, agglutinate fragments and a diverse clast inventory spanning the range of ferroan anorthosite and high magnesium suite rocks. Some of the basalt fragments in this sample are fractionated and have an igneous origin. However, the majority of the basalt fragments are impact melt clasts. PCA 02007 supports previous studies of feldspathic lunar meteorites that have suggested an aluminous crust for the Moon, with compositions more similar to magnesium granulite breccias than ferroan anorthosites. A 'chondrule-like' fragment found in PCA 02007 and unlike any previously described lunar material is described and tentatively identified as the remnants of a chondritic lunar impactor. This clast is porphyritic with equant olivines that have forsterite-rich cores (Fo(> 98)), extreme normal zonation to more fayalitic rims (Fo(> 44)), and a mineral assemblage with rare earth element abundances distinct from described lunar material and more similar to chondrules found in ordinary or carbonaceous chondrites. Its discovery and description is significant for understanding the composition of lunar impactors. Previously, the main evidence for chondritic lunar impactors was from chondritic relative abundances and near chondritic ratios of highly siderophile elements in lunar impact melt breccias. However, the presence of this clast, along with two other chondritic clasts from Apollo soils 12037 and 15602, provides clues to the identity of ancient meteorite impactors on the Moon. (c) 2006 Elsevier Inc. All rights reserved.